Aromatization of ethanol on Mo2C/ZSM catalysts

The reaction of ethanol was investigated on Mo₂C, Mo₂C/SiO₂ and Mo₂C/ZSM-5 catalysts at temperature ranging 573–973 K under atmospheric pressure. Mo₂C and Mo₂C/SiO₂ catalyzed only the decomposition of ethanol to H₂, ethylene, acetaldehyde and different hydrocarbons. The main reaction pathway on pure ZSM-5 is the dehydration reaction yielding ethylene, small amounts of hydrocarbons and aromatics. Deposition of Mo₂C on zeolite greatly enhanced the yield of benzene and toluene by catalyzing the aromatization of ethylene formed in dehydration process of ethanol.     

Conversion of methane to benzene over Mo2C and Mo2C/ZSM-5 catalysts

The activation and dehydrogenation of CH₂ on Mo₂C and MO₂C/ZSM-5 have been investigated under non-oxidizing conditions. Unsupported Mo₂C exhibited very little activity towards methane decomposition at 973 K. The main reaction pathway was the decomposition of methane to give hydrogen and carbon with a trace amount of ethane. Mixing Mo₂C with ZSM-5 support somewhat enhanced its catalytic activity, but did not change the products of the reaction. A dramatic change in the product formation occurred on partially oxidized Mo2C/ZSM-5 catalyst; besides some hydrocarbons benzene was produced with a selectivity of 70–80% at a conversion of 5–7%. Carburization of highly dispersed MoO₃ on ZSM-5 also led to a very active catalyst: the conversion of methane at the steady state was 5–6% and the selectivity of benzene formation was 85%.This laboratory is a part of the Center for Catalysis, Surface and Material Science at the University of Szeged.     

The oxidative dehydrogenation of ethane with CO2 over Mo2C/SiO2 catalyst

Mo₂C prepared on SiO₂ was found to be an effective catalyst for the dehydrogenation of ethane to produce ethylene in the presence of CO₂. The selectivity to ethylene at 850–923 K was 90–95% at an ethane conversion of 8–30%. With the increase of the temperature the dry reforming of ethane became also a significant process. It is assumed that the Mo oxycarbide formed in the reaction between CO₂ and Mo₂C plays an important role in the activation of ethane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation and reactions of CH3 species over Mo2C/Mo(111) surface

The reaction pathways of adsorbed CH₃ on the Mo₂C/Mo(111) surface were investigated by means of temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS). CH₃ fragments were produced by the dissociation of the corresponding iodo-compound. CH₃I adsorbs molecularly on Mo₂C at 90 K and dissociates at and above 140 K. The main products of the reaction of adsorbed CH₃ are hydrogen, methane and ethylene. The coupling into ethane was not observed. The results are discussed in relevance to the conversion of methane into benzene on Mo₂C deposited on ZSM-5. This revised version was published online in August 2006 with corrections to the Cover Date.     

Aromatization of pentane catalyzed over various metallosilicates

Various metallosilicates were synthesized using a hydrothermal method and characterized by SEM, XRD,²⁹Si MAS NMR, chemical analysis and surface area measurements. These results showed that they had a MFI structure. The pentane aromatization reaction was carried out over these metallosilicates in a continuous flow reactor at 550 °C, He/pentane=3, WHSV=1.5 h⁻¹ and 1 atm. Among the various metallosilicates, [Ga]ZSM-5(20) (52.3%) and [Zn]ZSM-5(40) (37.6%) showed higher aromatic selectivities for pentane aromatization. When [Al] ZSM-5(40) was ion-exchanged with gallium nitrate and zinc chloride, the selectivities for aromatics increased from 23.0% to 35.5% and to 32.7%, respectively. The Si/metal mole ratios of [Ga]ZSM-5 and [Al]ZSM-5 were changed from 20 to 250 and NH₃ temperature programmed desorption (TPD) was carried out. As the Si/metal ratio was changed from 250 to 20, the selectivities for aromatics were increased from 5.3 % to 52.3 % over [Ga]ZSM-5 and from 10.1% to 25.7% over [Al]ZSM-5. NH₃ TPD of [Ga]ZSM-5 indicated that the sites of medium acidity play an important role in the formation of aromatics. When H₂ and CO were added to the reactant of pentane, the production of methane and ethane increased and that of aromatics decreased.     

A novel Ni2Mo3N/MCM41 catalyst for the hydrogenation of aromatics

Bulk and MCM41-supported Ni₂Mo₃N catalysts were prepared using a temperature-programmed reduction (TPR) method and characterized using XRD, TEM, ICP-AES, and N₂ adsorption analysis techniques. Their catalytic properties were measured for the simultaneous hydrogenation of p-xylene and naphthalene and compared with Ni/MCM41 and Mo₂N/MCM41 catalysts having similar metal loadings. The results indicate that the Ni₂Mo₃N/MCM41 catalyst exhibits excellent deep hydrogenation activity under mild condition (T = 483 K, P = 3.0 MPa), and that it is more active than either Ni/MCM41 or Mo₂N/MCM41 catalyst.     

Effects of potassium on the chemisorption of CO2 and CO on the Mo2C/Mo(100) surface

The interaction of CO₂ with K-promoted Mo₂C/Mo(100) has been studied with high-resolution electron energy loss spectroscopy, work function measurements and temperature-programmed desorption. Pre-adsorbed potassium dramatically affects the adsorption behavior of CO₂ on the Mo₂C/Mo(100) surface. It increases the rate of adsorption, the binding energy of CO₂ and it induces the dissociation of CO₂ through the formation of negatively charged CO₂. Potassium adatoms also promote the dissociation of adsorbed CO over Mo₂C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of thermal treatment on states of molybdenum in Mo/H–ZSM-5 catalyst for methane dehydroaromatization: ESR and UV–VIS study

Valence and coordination states of molybdenum ions formed upon thermal treatment of Mo/H–ZSM-5 catalyst for methane dehydroaromatization in Ar and Ar/CH₄ media at 573–973 K have been studied by ESR and UV–VIS spectroscopy. For comparison, the characteristic ESR spectra of thermolyzed bulk ammonium heptamolybdate have been studied and analyzed in detail. The nature of earlier observed Mo⁵⁺ ions has been verified, and new paramagnetic states of molybdenum in Mo/H–ZSM-5 catalysts have been detected: Mo³⁺ ions, and Mo⁵⁺ ions in tetrahedral coordination with delocalization of unpaired electron to Al and H or Al and N atoms.     

Efficient H2 Production from Ethanol over Mo2C/C Nanotube Catalyst

Mo₂C deposited on silica is an effective catalyst for the decomposition of ethanol; the extent of the reaction approached 100% even at 623–673 K. Beside H₂ several C-containing compounds were produced, which caused the low yield of hydrogen. Preparation of Mo₂C by the reaction of MoO₃ with multiwall carbon nanotube, however, dramatically altered the product distribution. The formation of hydrogen came into prominence; about 40% of hydrogen content of ethanol decomposed at 523–723 K has been converted into H₂. Another feature of the Mo₂C/C nanotube is the relatively slow deactivation. Adding water to ethanol further enhanced the hydrogen production.     

Remarkable support effect of ZrO2 upon the CO2 reforming of CH4 over supported molybdenum carbide catalysts

In reforming of CH₄ with CO₂ over molybdenum carbide catalysts, the catalytic performance of unsupported hexagonal Mo₂C prepared by direct carburization of MoO₃ was considerably different from a similar composition, cubic MoC_1−x (x≈0.5), prepared through nitriding before carburization. The conversion levels over MoC_1−x were substantially higher than those over Mo₂C, although the turnover frequencies were lower. X‐ray diffraction analysis indicated that Mo₂C deactivated by conversion to MoO₂ during the reaction, but the MoC_1−x was transformed to the hexagonal Mo₂C and remained stable. The activity of Mo₂C dispersed on various supports for the CH₄–CO₂ reaction was also investigated. The performance depended strongly on the property of supports, with the ZrO₂‐supported Mo₂C catalyst exhibiting the highest activity and durability for this reaction. Moreover, deactivation of Mo₂C/ZrO₂ at ambient pressure was suppressed by decreasing the loading amount of Mo₂C. This revised version was published online in August 2006 with corrections to the Cover Date.     

CO2 and CO adsorption equilibrium on ZSM-5 for different SiO2/Al2O3 ratios

CO₂ and CO adsorption on MFI type zeolites with different SiO₂/Al₂O₃ ratios (ZSM-5(30), ZSM-5(50), ZSM-5(280), and silicalite) were investigated in this study by a static gravimetric analyzer for pure isotherms at 30°C, 65°C, 100°C, and 135°C over the pressure range of 0–10 atm. Adsorption capacity of CO increases with decreasing SiO₂/Al₂O₃ ratios within ZSM-5. The adsorption of CO₂ for decreasing SiO₂/Al₂O₃ ratios, showed stronger adsorption at lower pressures and at higher pressures, the highest capacity varied from ZSM-5(50) to ZSM-5(30). ZSM-5(280) was found to have the highest selectivity for CO₂ within the widest range of pressures and temperatures tested.     

Alkali-treatment of ZSM-5 zeolites with different SiO2/Al2O3 ratios and light olefin production by heavy oil cracking

Four kinds of ZSM-5 zeolites with different SiO₂/Al₂O₃ ratios are alkali-treated in 0.2 M NaOH solution for 300 min at 363 K. Changes to the compositions, morphologies, pore sizes, and distributions of the zeolites are compared before and after alkali-treatment. The changes observed are largely influenced by the SiO₂/Al₂O₃ ratios with which the zeolites are synthesized. A possible mechanism of desilication during alkali-treatment is proposed. The SiO₂/Al₂O₃ ratio of zeolites is found to influence the yield of light olefins that use heavy oil as feedstock. Alkali-treated ZSM-5 zeolites produce higher yields of light olefins compared to either untreated zeolites or the industry catalyst CEP-1. It is believed that alkali-treatment introduces mesopores to the zeolites and improves their catalytic cracking ability. ZSM-5 zeolites with SiO₂/Al₂O₃ ratios of 50 also present superior selectivity toward light olefins because of their optimized hierarchical pores.     

Construction of Dual-Shell Mo2C/C Microsphere towards Efficient Electromagnetic Wave Absorption

Carbon-based carbides have attracted tremendous attention for electromagnetic energy attenuation due to their adjustable dielectric properties, oxidation resistance, and good chemical stability. Herein, we reasonably regulate the growth of dopamine hydrochloride on the surface of the Mo-glycerate (Mo-GL) microsphere and then transform the resultant Mo-polydopamine (Mo-PD) microsphere into a dual-shell Mo₂C/C (DS-Mo₂C/C) microsphere in a high-temperature pyrolysis process under an inert atmosphere. It is found that the pyrolysis temperature plays an important role in the graphitization degree of the carbon matrix and internal architecture. The fabrication of a dual-shell structure can be propitious to the optimization of impedance matching, and the introduction of Mo₂C nanoparticles also prompts the accumulation of polarization loss. When the pyrolysis temperature reaches 800 °C, the optimized composite of DS-Mo₂C/C-800 exhibits good EM absorption performance in the frequency range of 2.0–18.0 GHz. DS-Mo₂C/C-800′s qualified bandwidth can reach 4.4 GHz at a matching thickness of 1.5 mm, and the integrated qualified bandwidth (QBW) even exceeds 14.5 GHz with a thickness range of 1.5–5.0 mm. The positive effects of the dual-shell structure and Mo₂C nanoparticles on EM energy attenuation may render the DS-Mo₂C/C microsphere as a promising candidate for lightweight and broad bandwidth EM absorption materials in the future.     

Synergic effect of Pd/γ-alumina and Cu/ZSM-5 on the performance of NO x storage reduction catalyst

NO _x reduction with a combination of catalysts, Pd catalyst, NO _x storage reduction (NSR) catalyst and Cu/ZSM-5 in turn, was investigated to elucidate for the high NO _x reduction activity of this catalyst combination under oxidative atmosphere with periodic deep rich operation. The catalytic activity was evaluated using the simulated exhaust gases with periodically fluctuation between oxidative and reductive atmospheres, and it was found that the NO _x reduction activity with this catalyst combination was apparently higher than that of the solely accumulation of these individual activities, which was caused by the additional synergic effect by this combination. The Pd catalyst upstream of the NSR catalyst improved NO _x storage ability by NO₂ formation under oxidative atmosphere. The stored NO _x was reduced to NH₃ on the NSR catalyst, and the generated NH₃ was adsorbed on Cu/ZSM-5 downstream of the NSR catalyst under the reductive atmosphere, and subsequently reacted with NO _x on the Cu/ZSM-5 under the oxidative atmosphere.     

The Effect of ppm-Level Na Impurity on the Structure of SiO2-Supported Mo Catalysts Prepared in a Clean Room

To investigate the effect of alkali impurity in Mo/SiO₂ on the MoO _x structure on SiO₂ surfaces SiO₂-supported Mo oxides were prepared with various amounts of Na ions in a class-1 clean bench with a laminar flow in a class-1000 clean room. The Na concentrations were varied in the range 0-5000 ppm, while the Mo loading on SiO₂ was maintained at 0.7 wt%. The Mo-Na/SiO₂ samples obtained were characterized by diffuse reflectance UV-visible and Raman spectroscopy. Three types of Mo species were identified: octahedral monooxo Mo monomer species, Na₂Mo₂O₇ and MoO₃. At less than 100 ppm Na both octahedral Mo monomers and MoO₃ species were formed on SiO₂. The MoO₃ species was transformed to Na₂Mo₂O₇ at 2000 ppm Na, where the Na ions interact directly with the Mo species on the surface. The octahedral monooxo Mo monomer species seems not to be influenced significantly by Na impurity.     

Co-decorated carbon nanotube-supported Co–Mo–K sulfide catalyst for higher alcohol synthesis

Using chemical reduction-deposition method, a type of metallic cobalt-decorated multi-walled carbon nanotubes, noted as y%(mass percentage)Co/MWCNTs, was prepared. TEM, SEM and XRD measurements demonstrated that the metallic cobalt was evenly coated on the MWCNT substrate, with granule-diameter of the Co _x ⁰ -crystallites of 5–8 nm. Using the y%Co/MWCNTs as support, a type of supported Co–Mo–K sulfide catalysts, noted as x%(Co _i Mo _j K _k )/(y%Co/MWCNTs), for higher alcohol synthesis (HAS) was developed. It was experimentally shown that using the Co-modified MWCNTs in place of simple MWCNTs or activated carbon (AC) as the catalyst support led to a significant increase in activity of CO hydrogenation conversion and improvement in the selective formation of C₂₊-alcohols. Under the reaction condition of 5.0 MPa, 613 K, CO/H₂/N₂ = 45/45/10 (v/v) and GHSV = 3600 ml_STPh⁻¹ g _−cat. ⁻¹ , the observed STY of C_1–4-alcohols reached 154.1 mgh⁻¹g _−cat. ⁻¹ at 12.6% conversion of CO over the 11.6%(Co₁Mo₁K_0.6)/(6.4%Co/MWCNTs) catalyst, which was 1.76 and 2.33 times as high as that (87.7 and 66.1 mgh⁻¹g _−cat. ⁻¹ ) of the reference systems supported by simple MWCNTs and AC respectively. Ethanol became the predominant product of the CO hydrogenation, with carbon-based selectivity ratio of C_2–4-alcohols to CH₃OH reaching 3.6 in the products. It was experimentally found that using the Co-modified MWCNTs in place of simple MWCNTs or AC as the catalyst support caused little change in the apparent activation energy for the conversion of CO, but led to a slight increase in the molar percentage of catalytically active Mo-species (Mo⁴⁺) in the total Mo-amount at the surface of the functioning catalyst. Based upon the results of TPD investigation, it could be inferred that, under the reaction condition of HAS, there existed a considerably larger amount of adsorbed H-species and CO-species on the functioning catalyst, thus in favour of increasing the rate of a series of surface hydrogenation reactions in HAS.     

In situ production of nickel/graphitic carbon nanofiber composites and application in catalytic hydrodechlorination

The action of Ni/SiO₂ in the gas phase hydrodechlorination (at 573 K) of chlorobenzene, 1,3-dichlorobenzene and 1,3,5-trichlorobenzene is compared with that of a Ni/SiO₂ + C composite. The latter was prepared in situ by the decomposition of chlorobenzene at 873 K to generate graphitic carbon nanofibers bearing Ni particles at the fiber tips. The Ni/SiO₂ and Ni/SiO₂ + C (with varying C content) catalysts have been characterized by TEM, SEM, XRD and H₂ chemisorption. While the Ni/SiO₂ + C system delivered a lower initial fractional dechlorination, the composite outperformed the starting Ni/SiO₂ in terms of long-term activity, an effect that is linked to the structural characteristics.     

n-Octane aromatization on Pt-containing non-acidic large pore zeolite catalysts

Platinum catalysts supported on the potassium-form of different large-pore zeolites (i.e. K-LTL, K-BEA, K-MAZ, and K-FAU) have been tested for n-octane aromatization at 500 °C. All catalysts were prepared by the vapor phase impregnation (VPI) method. It was found that the Pt/K-LTL catalyst exhibit a better aromatization performance than the other zeolite catalysts. However, due to secondary hydrogenolysis, the C8 aromatics produced inside the zeolite are converted to benzene and toluene. By contrast, a non-microporous Pt/SiO₂ catalyst did not present the secondary hydrogenolysis. Therefore, despite a lower initial aromatization activity, Pt/SiO₂ results in higher selectivity to C8 aromatics than any of the other zeolite catalysts. All fresh catalysts were characterized by hydrogen chemisorption and FT-IR of adsorbed CO. In addition, the residual acidity of the supports was analyzed by temperature programmed desorption (TPD) of ammonia. In agreement with previous studies, it was found that after reduction at either 350 or 500 °C, the Pt/K-LTL showed much higher Pt dispersion than other catalysts. It is known that the structure of L zeolite can stabilize the small Pt clusters inside the zeolite channel. By contrast, FT-IR indicated that a large fraction of platinum clusters were located outside the zeolite channels in the case of Pt/K-BEA and Pt/K-MAZ catalysts.     

Study of the Supported K2MoO4 Catalyst for Methanethiol Synthesis by One Step from High H2S-Containing Syngas

ESR and XPS are used to study the Mo-based catalysts MoO₃/K₂CO₃/SiO₂ and K₂MoO₄/SiO₂ prepared with two kinds of precursors, (NH₄)₆Mo₇O₂₄4H₂O and K₂MoO₄. The catalytic properties of the catalysts for methanethiol synthesis from high H₂S-containing syngas are explored. The activity assay shows that the two catalysts have much the same activity for the reaction. By the ESR characterization of both functioning catalysts, the resonant signals of oxo-Mo(V) (g=1.93), thio-Mo(V) (g=1.98) and S (g=2.01 or 2.04) can be detected. In the catalyst MoO₃/SiO₂ modified with K₂CO₃, as increasing amounts of K₂CO₃ are added, the content of oxo-Mo(V) increases, but thio-Mo(V) decreases. The XPS characterization indicates that Mo has mixed valence states of Mo⁴⁺, Mo⁵⁺ and Mo⁶⁺, and that S includes three kinds of species: S^2– (161.5 eV), [S–S]^2– (162.5 eV) and S⁶⁺ (168.5 eV). Adding K₂CO₃ promoter to the catalysts, the Mo species of high valence state is easily sulphided and reduced to Mo₂S and oxo-M(V), and the derivation of [S–S]^2– and S^2– species from S is promoted simultaneously. The methanethiol synthesis is favored if the mole ratio of (Mo⁶⁺ + Mo⁵⁺)/Mo⁴⁺ 0.8 and S^2–/[S–S]^2– is kept at a value of about 1.     

Skeletal isomerization of 1-butene over ferrierite and ZSM-5 zeolites: influence of zeolite acidity

Three ferrierite (FER) and five ZSM-5 (MFI) zeolites with SiO₂Al₂O₃ ratio ranging from 27 to 2000 are tested as catalysts for the skeletal isomerization of 1-butene at 350–450°C and atmospheric total pressure in order to study the influence of acidity and pore structure of zeolite on conversion and selectivity. The catalytic and NH₃ temperature-programmed desorption results from FER and MFI catalysts with the same SiO₂/Al₂O₃ ratio reveal that the pore structure of FER zeolite rather than its acidity may play an important role in achieving high selectivity for the skeletal isomerization of 1-butene to isobutene.